In this study, impacts of toxic ions/acids found in real fermentation-hydrolysate on the model exoelectrogenic G. sulfurreducens were investigated. Initially, different concentrations of acetate, butyrate, propionate, Na+, and K+ were tested, individually and in combination, for effects on the planktonic growth, followed by validation with diluted-hydrolysate. Meanwhile, it could be shown that (1) excess Na+ (≥100 mM) causes inhibition that can be reduced by K+ replacement, (2) butyrate (≥10 mM) induces higher toxicity than propionate, and (3) hydrolysate induces synergistic inhibition to G. sulfurreducens where organic constituents contributed more than Na+. Afterwards, compared with impacts on planktonic cells, the pre-enriched anodic biofilm of G. sulfurreducens in BESs showed higher robustness against diluted-hydrolysate, achieving current densities of 1.4-1.7 A/m2 (at up to ∼30 mM butyrate and propionate as well as ∼240 mM Na+). As a conclusion, using G. sulfurreducens in BESs dealing with fermentation-hydrolysate can be regulated for efficacious energy recovery.